Method of producing sulphonic acids and salts thereof



Patented Aug. 29, 193% METHOD OF PRODUCING SULPHONIO ACIDS AND SALTS THEREOF Walther Schranth, Berlin-Dahlem,

and Eric Schirm, Dessau, Germany, assignors, by mesne assignments, to Unichem Ohemikalien Handels A.-G., Zurich, Switzerland, a corporation of Sweden No Drawing.

Application December 31, 1930,

Serial No. 505,975. In Germany September 29,

'7 Claims. (Cl. 260-513) This invention relates to processes for preparing high molecular weight sulphonic acids.

It has been found, that excellent wetting-out-, emulisfying-, dispersiom, peptisationand cleansing agents are produced by treating the mineral acid esters or ester salts, for instance the halogen-hydric acid esters or sulphuric acid ester salts, of higher molecular monoor polyvalent aliphatic or hydrocyclic saturated or un- .i saturated alcohols with a primary alcohol group,

such as may be obtained from natural Waxes by splitting or reducing (hydrogenating) them, or from natural fats, fatty acids or similar esters, or from hydrocyclic carboxylic acids, as for :instance naphthenic acids or their esters, by

reducing them with hydrogen, with neutral salts of sulphurous acid, as for instance sodium-, potassium-, ammonium sulphite at raised temperatures, preferably in the presence of an inert diluent with or without pressure. In some cases agents accelerating the reaction are added, such as for instance alkaline iodides.

It is already known, that alkyl halides and salts of alkyl sulphuric acids may be converted by alkaline sulphites to alkyl sulphonic acids. But this reaction has been carried out hitherto only with the lower members of the aliphatic series, where the greater solubility and time of reacton are favorable to the reaction. But it could not be concluded therefrom, that the above mentioned conversion might be carried out also in the higher ranks with the necessary velocity and with satisfactory yields, to form the basis of a technically applicable process. There may be mentioned in the contrary numerous examples proving, that reactions, (as for instance the so called destruction-process of Hofmann of the carboxylic acid amides to the following lower amines), successfully carried out in. the lower ranks are not applicable to the higher series. And finally it is completely new, that the above mentioned reaction could be carried out also in the hydrocyclic ranks. Also the herewith produced technical effect was hitherto unknown.

Although we may arrive-*according to prior art-at sulphonic acids of the aliphatic series also by means of direct sulphonation of the hydrocarbons, it has to be considered, that those products are different from the products as produced according to this specification. Quite apart from: the fact, that it is not possible without difficulty to sulphonate aliphatic and hydrocyclic hydrocarbons, and that side-reactions cannot be avoided, which interalia cause an undesirable discoloration of the finished products,

the sulphonation products of the hydrocarbons are compounds of various types with a more or less higher degree of sulphonation and of unknown constitution, because also in this case the sulphonation cannot be carried out uniformly, as the hydrocarbon-chain is attacked at different atoms. In contrast therewith the sulphonic acids as produced according to the procedure of this specification contain a sulpho-group affixed to the last carbon atom of the chain. The conclusion has been reached, that just this condition cannot be dispensed with, if we want to bring forth those especially characteristic, technically valuable capillary active properties of these substances.

Example 1 Cetyl alcohol which may be obtained from saponified cetaceum (spermaceti), is converted according to methods already known, for instance by means of gaseous hydro-bromic acid, into the cetyl bromide. Then 305 part of the above product are brought into the tripled quantity of alcohol 70-80%, into which have been passed before, by cooling the whole, 51 parts of ammonia and 96 parts sulphur dioxide. The whole mixture is heated up to 120-129 C. in an. autoclave until the cetyl bromide has completely disappeared. Thereupon sodium lye is added in such a quantity, that an alkaline reaction occurs and the whole mass is evaporated to dryness. The residue is extracted with hot alcohol (absol.). There remains after evaporating the alcoholic solution of the sodium salt of cetyl sulphonic acid.

The soaplike product may be used especially for finishing textiles and besides in all cases, where strong emulsifying agents are applied.

Example 2 A mixture of the higher aliphatic primary alcohols, as may be obtained by catalytical highpressure-hydrogenation of coconut oil or its fatty-acids, or by reduction with sodium and alcohol of cocoa-fatty-acid-esters or cocoa-fat itself, is converted in the usual manner with chlor-sulp-honic acid at low temperature into the alkyl-sulphuric acids. These are cooled down and introduced into the calculated quantity of sodium lye 40%. Alcohol corresponding in quantity with the existing water and a concentrated solution of potassium-sulphite in excess are then added to the pasty mass. Then the mixture in an agitator autoclave is heated up to 130-180 C. until the conversion is completed, a

from the residues the salts of the alkyl-sulphonic acids with alcohol.

The yielded product possesses an excellent lathering-wetting-outand cleansing efiiciency, causing no precipitation with calciumor magnesium salts and therefore is able to form a valuable soap-body especially applicable for the uses of textile-industry. Furthermore it may be used in all such cases, where Turkey-red-oil is applicable and especially where high sulphonated Turkey-red-oil is used. In consequence itv may be used also for producing solutions and emulsions of fats and oils of all kinds, organic solvents etc. for numerous technical purposes.

Example 3 Naphthenic acids of the fraction boiling at 70 to 140 C. at mm. pressure are treated with hydrogen under high pressure in the presence of suitable catalysts, or are reduced in the form of their esters with sodium and butylalcohol. The mixture of the resulting primary naphthenyl alcohols is esterified in the usual way. The resulting naphthenylic chlorides then are heated with neutral sodium sulphite in a moderate ex cess (calculated on the average molecular weight of the naphthenylic chlorides) by adding a certain quantity of 50% alcohol, corresponding to the weight of the chlorides plus sulphite, and 1% sodium-iodide, in an autoclave while stirring, until all the chlorine is in such a form that it may be ionized. Then alcohol and water are removed by distillation and the residues are used either directly or as the sodium salts of the naphthenyl sulphonic acids after being separated as mentioned before by extracting with alcohol and vaporising the alcoholic solution. The yielded product possesses an excellent wettingout property and may be used in the same way as the substances produced according to Examples 1 and 2 for numerous purposes of textileleathersoappaper and rubber industries.

We claim:

1. In the process of producing higher molecular sulphonic acids, the step which consists in converting a sulphuric acid acid ester of a higher molecular alcohol to a salt of a sulphonic acid by treatment first with sodium hydroxide to fact, which may be recognised, if the sulphuricform a sodium ester salt and thereafter with potassium sulphite to obtain the salt of the suphonic acid.

2. The method of producing salts of higher molecular sulphonic acids which comprises converting a higher molecular alcohol to a sulphuric acid acid ester and converting the ester to a salt of sulphonic acid by treatment with sodium hydroxide and a sulphite of the group consisting 'of potassium, ammonium and sodium sulphites.

3. The method of producing salts of higher molecular sulphonic acids in which the sulpho group is aiflxed to the end carbon atom of the chain, which comprises converting a higher molecular primary aliphatic alcohol to a bromide, dissolving the bromide in approximately '70 to 80% alcohol containing ammonium sulphite in solution, in a ratio of approximately one part of bromide to three parts of alcohol, and heating the mixture to a temperature approximately 120 to 124 C. in an autoclave to convert the bromide to a salt of sulphonic acid.

4. The method of producing cetyl sulphonic acid which comprises converting cetyl alcohol to cetyl bromide, dissolving ammonia and sulphur dioxide in 70-80% alcohol and dissolving the bromide in a larger quantity of said alcohol and heating the whole to approximately 120 to 124 C. in an autoclave to convert the bromide to cetyl sulphonic acid.

5. The method of producing salts of sulphonic acids which comprises converting unsaturated high molecular alcohols of the type obtained from natural fats and waxes into mineral acid esters, reacting the mineral acid esters with a neutral salt of sulphurous acid at a high temperature to form salts of sulphonic acids.

6. The method of producing salts of sulphonic acids which comprises reacting alcohol obtained from cocoanut oil with mineral acid to form mineral acid esters, neutralizing the product with sodium hydroxide and reacting the product With neutral salt of sulphurous acid at a high temperature and in the presence of a diluent.

7. The method of producing salts of sulphonic acids which comprises converting high molecular alcohols as obtained from the natural fats and waxes by catalytic reduction into minteral acid esters and reacting the mineral acid esters with a neutral salt of sulphurous acid.

WALTER SCHRAUTH. ERIC SCHTRM.

CERTIFICATE OF. CORRECTION. Patent No. 2,171,117; v August 29, 1939; 3

- WALTHER SGHRAUTH, ET AL.

It is hereby certified that the country of incorporation of the assignee in the above numbered patent was erroneously described and specified as "Sweden" whereas said country of incorporation should have been described and specified as Switzerland, as shown by the record of assignments in this office; and that the said Letters Patent shouldbe read with this correction therein, that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 7th day of November, A. D. 1959.

Henry Van Aredale, (Seal) Acting Commissioner of Patents. 

